BKC3492

TRANSPORT PROCESSES AND UNIT

OPERATION II
Unit Operation

Crystallisation

Introduction
Crystallisation is solid-liquid separation process, in which mass

transfer of a solute from the liquid solution to a pure solid

crystalline phase occurs.
Can occurs in
the freezing of water to form ice
the formation of snow particles from a vapour
the formation of solid particles from a liquid melt
the formation of solid crystals from a liquid solution

Commercial crystallization (i.e. production of sugar, MSG, NaOH-home

salt)
Yield and purity
Shape and size uniform
Avoid caking
Ease of pouring
Ease in washing and filtering

Types of Crystal Geometry

Crystal is a solid composed of atoms, ions, or molecules which are arranged in an
orderly and repetitive manner. It is a highly organised type of matter. The
atoms, ions or molecules are located in 3D arrays or space lattices.
Crystals appear as polyhedrons having flat faces and sharp corners. The relative
sizes of the faces and edges of different crystals of the same material may
different greatly. However, the angles between the corresponding faces of all
crystals of the same material are equal and are characteristic of that particular
material. Therefore, crystals are classified on the basis of these interfacial angles.

7 classes of crystals,

Cubical system
Tetragonal system
Orthorhombic system
Hexagonal system
Monoclinic system
Triclinic system
Trigonal system

Equipment for crystallization

Crystallization equipment can be classified

according to

Method used to bring supersaturation

Supersaturation produced form cooling the solution with
negligible evaporation
Tank and batch type crystallizers
Solubility curves decrease markedly with temperature

Supersaturation produced by evaporation of solvent with little or

no cooling
Evaporator crystallizers
Solubility curve changes little with temperature

Supersaturation by combined cooling and evaporation in an

adiabatic evaporators
adiabatic evaporator-vacuum crystallizers
Hot solution is introduced into a vacuum, solvent evaporates and the
solution is cooled adiabatically

Types of crystalliser

Types of crystalliser

Yield and Heat and Material Balance in

Crystallization

What happen to the solubility if temperature increases?

Example 12.11-1
A salt solution weighing 10000 kg with 30 wt % Na2CO3 is cooled to 293 K (20'C). The salt crystallizes as the
decahydrate. What will be the yield of Na2CO3. 1 0H2O crystals if the solubility is 21.5kg anhydrous N a2CO3/10k0g of total water? Do this for the
following cases:
(a) Assume that no water is evaporated.
(b) Assume that 3%of the total weight of the solution is lost by evaporation of water in cooling.

Solution:
1- the molecular weights are 106 for Na2CO3 , 180 for 10H2O and 286.2 Na2CO3. 10H2O.
2- the process flow diagram is shown in figure 12.11-2 with W being kg H2O evaporated , S kg
solution (mother liquor) and C kg crystal of Na2CO3. 10H2O
3- Making a material balance around the dashed line box for water for part (a) , where W=0
0.7(10000)= (100/(100+21.5)*S)+((180.2/286.2)*C)+0
Where (180.2/286.2) is the wt fraction of water in the crystals . Making a balance for Na2CO3
0.3 (10000)= (21.5/(100+21.5)*S)+(106/286.2)*C+0
Solving the two equations
C=63701 kg Na2CO3 .10H2O
S = 3630 kg solution
For part (b) W=0.03(10000) = 300 kg H2O
Using equation (12.11-1)
0.7(10000) = (100/(100+21.5)*S)+(180/286)C+300
Solving equations 12.11-2 and 12.11-3
C=6630 kg of Na2CO3 .10H2O
S= 3070 kg solution

HEAT EFFECTS AND HEAT BALANCES IN CRYSTALLIZATION

When a compound whose solubility increases as the temperature increases dissolves , there is an
absorption of heat , called the heat of solution.
An evaluation of heat accurse when the compound dissolves whose solubility does not change with
temperature , there is no heat evolution on dissolution .
In crystallization the opposite of dissolution occurs . At equilibrium the heat of crystallization is equal to
the negative of the heat of solution at the same concentration in solution .
With many materials this heat of dilution is small compared with the heat of solution , and this
approximation is reasonably accurate.
The most satisfactory method for the calculating heat effects during a crystallization process is to use the
enthalpy-concentration chart for the solution and various solid phases which are present for the system.
Few charts are available for some materials and systems
The enthalpy H1 is kJ for the total feed , the enthalpy H2 of the final mixture of crystals and another liquor
at the final temperature is also read off the chart.
If some evaporation accurse , the enthalpy Hv of the water vapor is obtained from the steam tables. Then
the total heat absorbed q in kJ is
q = (H2 + Hv) H1
SEE EXAMPLE 12.11If q is positive . Heat must be added to the system
2
If q is negative . Heat must be given off the system

Crystallisation Theory

Nucleation theory
Nucleation is number of new particles formed per unit time per unit
volume of mother liquor
Solubility and crystal size
Solubility refers to the ability for a given substance, the solute, to
dissolve in a solvent. It is measured in terms of the maximum amount
of solute dissolved in a solvent at equilibrium. The resulting solution is
called a saturated solution.
Smaller crystal is better
Solubility of small crystal better
Homogeneous nucleation
High supersaturation and no agitation
Result of random fluctuations of molecules in homogeneous solution
Contact nucleation
With agitation
Formation of nuclei occurs in collision between crystals
Formation of nuclei due to interference of the contacting agent (walls of
a container or agitator blades)

Rate of crystal growth L Law

The rate of growth of a crystal face is a distance move per unit time in a
direction that is perpendicular to the face. Crystal growth is layer-by-layer
process.
Particle size distribution of crystal and since growth can occur only at the outer
face of the crystal , the solute material must be transported to that face from
the bulk of the solution .
The solute molecules reach the face by diffusion through the liquid phase. The
usual mass transfer coefficient ky applies in this case.
The equation for mass transfer of solute A from the bulk solution of supersaturation concentration yA , mole fraction of A, to the surface where
the concentration is yA is

Where ky is the mass transfer coefficient in kg mol/s.m

Where ks is a surface reaction coefficient in kg mol/s.m2

Where K is the overall mass transfer coefficient.

NOTE
1- when the mass transfer coefficient ky is very large , the surface reaction is
controlling and 1/ky is negligible .
2- when the mass transfer coefficient is very small , diffusional resistance is
controlling .

The L law for crystal growth :

It was shown that all crystals that are geometrically similar and of the same
material in the same grow at the same time .
Growth is measured as the increase in the length L , in mm .
Mathematically the law of crystal growth can be written as:
L/t = G

Where
t = time in h and growth rate G is a constant in mm/h

 Particle size distribution of crystal

An important factor in the design of any crystallizer is
the size of the crystal formed or the size distribution of
the crystals.
One of the standard methods in the size distribution
estimation is by using the sieve analysis technique .
(please see appendix A.5-3.)
The common parameter used to characterize the size
distribution is the coefficient of variation CV
CV = 100*[(PD16% - PD84%)/2PD50%]

Where:
PD = particle diameter at 16% retained

 Model for mixed suspension-mixed product removal

crystallizer

One of the most important types of the models used in the crystallization is
what is called (mixed suspension-mixed product removal crystallizer ,
(MSMPR).

To analyze the data from a crystallizer , an overall theory must consider

combining the effects of nucleation rate , growth rate , and material balance.
Randolph and larson derived such model. They plotted the total cumulative
number of crystals N per unit volume of suspension (usually 1L) of the size L
and smaller versus the size L as in Fig 12.12-2

The slope dN/dL of this line is denied as a crystal population density n:

Where n is the number of crystals /(L.mm).

n= dN/dL

This population density is obtained experimentally by screen analysis of the total crystal content of a
given volume
Each sieve fraction by weight is obtained by collection between two closely spaced and adjacent
screens. Then
Lav = (L1+L2)/2
L1 & L2= the openings in mm in the two adjacent screens

Population material balance:

Average particle size and nucleation rate

Prediction of cumulative weight fraction obtained

EXAMPLE 12.12-1 Growth of nucleation rates in MSMPR crystallizer

Calculate the population density and nucleation growth rates for crystal samples
of urea from screen analysis . The slurry density (g of crystals) is 450g/liter , the
crystal shape factor a is 1.00 , the crystal density is 1.335 g/cm3 , and the
resistance time is 3.38 h . The screening analysis from reference B5 is as follows :

Solution
1. The data above are tabulated in table 12.12-1 using data from appendix
A.5-3.
2. The value of L is the screen opening
3. For the 14-20 mesh portion , Lav = (1.168+0.833) /2 = 1.001 mm
L = 1.168 0.833 = 0.335 mm
4. For Lav = 1.001 mm using equation (12.12.8) ,
vp = aLav3 = 1.00(1.001)3 = 1.003 mm3/particle
5. The mass particle = .vp = 1.335*10-3(1.003) = 1.339*10-3 G
6. The total mass crystals = (450 g/L)(0.044 wt.fr)
7. Using equation (12.12-9) to calculate n for the 14-20 mesh size range,
n= (N/ L) = (450g/L)(wt frac)/((aL)3. L)
= 4.414 * 104 number of crystals /L.mm

8. Then ln n = ln 4.414*104 = 10.695

9. For the 20-28 mesh size range , Lav = 0.711/mm , and L = 0.244 , then
n = ((450*0.144)/(1.335*10-3 *1.00*(0.711)3*0.244))
= 5.535*105
Then ln n = 13.224
10. The ln n is plotted versus L in figure 12.12-3 . The equation of this line is
equation 12.12-14 , where the slope is (-9.12) and intercept = 19.79

11. The slope -9.12 = -1/G = -1/(G)(3.38) . Hence , G= 0.03244 mm/h .

12. The intercept ln no=19.79. Hence , no = 3.933*108. from equation 12.12-18 .
The nucleation rate Bo is
Bo = Gon = 0.03244(3.933*108) = 1.27 * 107 nuclei/h.L
The average size is , from equation 12.12-15 , La = 3.67G = 3.67(0.03244)
(3.38) = 0.402 mm
The predominant size , from equation 12.12-16 , is Ld = 3.00 G =
3.00(0.03244)(3.38) = 0.329 mm